New dioxazine dyestuffs and process for their manufacture



-atent fihce 3,065,229

Patented Nov. 20, 1952 cals there may be mentioned acylamino groups which ,229 contain the radicals of the following carboxylic acids: NEW DIOXAZINE DYESTUFFS AND PROCESS non THElR MANUFACTURE Bellow Held, Karl Ronco, Muttenz, Switzerland, assignor to 4'Ihethy1-hehZ01e acid,

Ciba Limited, Basel, Switzerland 5 2-fluoro-benzoic acid, No Drawing. Filed June 13, 1960, Ser. No. 35,459 2-chloro-benzoic acid, Claims priority, application Switzerland June 23, 1959 4 chloro benzoic acid,

Claims- 2:4-dichloro-benzoic acid,

2 S-dichloro-benzoic acid, 4-bromo-benzoic acid, 4-phenyl-benzoic acid, 4-methoxy-benzoic acid, 3-methoxy-benzoic acid,

This invention provides new dioxazine dyestufis of the general formula 4-cyano-benzoic acid, A l A 4-nitro-benzoic acid,

NW 0 lor 2-naphthoic acid.

X The radical R may also represent a polycyclic aromatic radical, for example, a naphthalene, anthracene or pyrene in which each A represgnts an aryl radical, advanta radical. In order to bring about ring closure to form the geously a benzene radical, and each X represants an oxazine ring the aforesaid starting materials are treated acyloxy or more especially an acylamino grou with a non-sulfonatmg condensing agent. As such agents The invention also provides a process for the manufacthere may be mennened for example sulfuric acid, ture of the dyestuffs of the above general formula, wherein Fnedel'craftsi catalysts, alumiflem chloride a quinone f h general f l or iron chloride, and especially aromatic acid chlorides, for example, benzoyl chloride or naphthoyl chloride, (2) X benzotrichloride or benzene sulfochloride. The reaction is advantageously carried out in a high boiling inert or- 0 NH R ganic solvent, for example, nitrobenzene, mono-, dior L tri-chlorobenzene, naphthalene or a-chloronaphthalene RnHN at a raised temperature.

I The dyestufis of the Formula 1 are valuable red to blue pigments of good fastness to light, which can be in which each X has the meaning given above, and the used for all purposes for which pigments are customarily symbols R represent diiferent or preferably identical used, for p so-ealled Pigment Priming, that aromatic radicals free from acid groups imparting soluis to say, the printing process in which the pigment is bility in water, is treated with a non-sulfonating confid 011 a substratum, especially on a textil fiber, 011 densing agent. another flat structure such as paper (for example wall The compounds of the Formula 2 used as starting mapaper), or fabrics of glass fibers, by means of a suitable terials are advantageously obtained by condensing One adhesive such as casein, a hardenable synthetic resin, mol of a para-benzoquinone of the formula more especially urea-formaldehyde or melamine-formaldehyde condensation products, solutions or emulsions of (3) f polyvinyl chloride or polyvinyl acetate or other emulsions, for example, oil-in-water or water-in-oil emulsions. O 01 The pigments can also be used for other purposes, for example, in finely dispersed form for dyeing artificial C1 0 silk from viscose or cellulose ethers or esters, or of polyamides or polyurethanes in the spinning mass, and also X for making colored lacquers or lacquer formers, solutions in which each X has the meaning given above with two and products of acetyl-cellulose, nitrocellulose, natural mols of an arylamine, advantageously an aminobenzene resins or synthetic resins, such as polymerization resins,

In the compounds of the Formula 2 used as starting for F P P Y Y chlorlde f polystyrene, or conmaterials, X advantageously represents an acylamino densatlon resms for example e e i fe group derived from an aliphatic or cycloaliphatic monopolyethylene polya'cryl gums casem elheones and carboxylic acid containing at most 8 carbon atoms, for e resms' They 'f also be used wlth advantage e example an acetylamino propiohylamino or butyryh making colored penc1ls, cosmetic preparations and lam1- amino group or an acyloxy group, for example, an acetoxy mated e or propionoxy group. As aromatic radicals there may Owmg to h ehemleahmlertnese and good h be mentioned more especially benzene radicals, and prefslstanee the Plgments P thls ye can be dlsPersed erably those which contain in ortho-position to the imino by the P l methods In eemposltlons or Products of t group an alkoxy group. Furthermore the benzene radical aferesald f 'l and advantageously at a Stage at Whleh may contain f h substituents, f example, halogen the compositions or products have not reached their final atoms, especially chlorine, or alkyl groups, for example, form; e ep q h' e p g Such as Spinning methyl groups or aryl radicals, for example, phenyl P 8 P h eastlng, Stieklhg and h like, can Then groups, or alkoxy groups, for example, methoxy, ethoxy be earned out In the Presence of the plgmehtsor isopropoxy groups, nitro groups, or acylamino groups, When the Pigments have not Previously been brought for example, acetylamino, naphthoylamino or benzoyI- into a finely dispersed form and/or into the modification amino groups which latter groups may be substituted i especially suitable for use, it is necessary to subject them the benzene radical, for example, by halogen atoms or before US a Conditioning treatment, p y alkyl, alkoxy, nitro, cyano, acylamino, arylamino or grinding them in the y aqueous Wet State, advah' phenyl groups. As examples of suitable acylamino raditageously in the presence of an organic water-soluble or water-insoluble solvent or by kneading or grinding the crude pigment in the presence of a solid assistant, for example, a salt capable of being removed by washing. A combination of the different methods may also give good results. In many cases it is an advantage, for the purpose of converting it into a finely dispersed form, to grind the crude pigment with the substratum to be colored or with a component of the substratum.

The pigments are distinguished by their very good fastness to migration, which is substantially better than that of dioxazine dyestuffs which contain a hydrogen atom or a halogen atom instead of the substituent X.

The following examples illustrate the invention, the parts and percentages being by weight.

Example 1 A mixture of 45 parts of -1-amino-2-methoxy-4-benzoylamino--isopropoxybenzene, 18 parts of 2:5-diacetylamino-3:6-dichloroquinone and parts of anhydrous sodium acetate in 500 parts of ethanol is refluxed at the boil for 7 hours, suction-filtered while still hot, and the filter residue is washed with hot ethanol and then with water and dried. The resulting brown powder is the 2:5- diacetylamino 3:6 bis (2'-methoxy-5-isopropoxy-4'- benZoylamino-phenylamino)-l :4-benzoquinone.

A mixture of 16.4 parts of this product, 6 parts of benzoyl chloride and 300 parts of ortho-dichlorobenzene is heated for 5 hours at 170-175 C. At 100 to 120 C. the pigment is suctioned off, successively Washed with hot ortho-dichlorobenzene, hot alcohol and hot water and then dried. The resulting dyestuff of the formula NHCO CH3 CH3 NHCOOHa Example 2 A mixture of 6 parts of 2:5-diacetylamino-3:6-dichloroquinone, 12.5 parts of 1-amino-4-benzoylamino-2:5- diethoxybenzene, 3.4 parts of anhydrous sodium acetate and 500 parts of ethanol is refluxed for hours, filtered while still hot, then successively washed with ethanol and water and the residue is dried at 100 C. The reddish brown powder obtained in this manner is the 2:5-diacetylamino-3:6 di-(2.:5-diethoxy- 4 benzoylaminophenylamino -1 :4-benzoquinone.

A mixture of 12.3 parts of this product, 600 parts of ortho-dichlorobenzene and 4.2 parts of benzoyl chloride is heated for 5 hours at 170175 C. At 100 to 120 C. the pigment is suctioned oft, successively washed with hot ortho-dichlorobenzene, hot alcohol and water and then dried. The resulting 2:6-dibenZoylamino-3:7-diethoxy- 9:10-diacetylamino-triphene-dioxazine is a greyish blue powder which in the finely dispersed state colors polyvinyl chloride foils strong bluish violet tints of very good fastness to migration and light.

Examples 3 to 5 The following table lists further products of similar properties, obtained as described above. The base used instead of 1-amino-4-benzoylamino-2zS-diethoxybenzene is, shown in column I, while column II gives the tint of polyvinyl chloride foils colored with the dioxazine pigment.

Example 6 A mixture of 9 parts of 2:5-diacetylamino-3z6-dichloroquinone, 19.2 parts of l-amino-4-benzoylamino- 2:5-dimethoxybenzene, 5.1 parts of anhydrous sodium acetate and 500 parts of ethanol is refluxed for 10 hours, then filtered while still hot, then Washed with ethanol and then with water and the residue is dried at C., to yield 2 5 -diacetylamino-3 :6-di-(2 5-dimethoxy-4-benzoylamino-phenylamino)-1:4-benzoquinone as a reddish brown powder.

A mixture of 11.4 parts of this product, 4.2 parts of benzoyl chloride and 500 parts of ortho-dichlorobenzene is heated for 5 hours at to C., filtered, and successively washed with hot ortho-dichlorobenzene, hot alcohol and water, to yield 2:6-dibenzoylamino-3:7-dimethoxy 9:10 diacetylamino-triphene-dioxazine of the formula NHCOCH: W HaCO- 1 NHCOCaH: C(tHsCOHN- OCHa NH0 0 CH3 as a reddish violet powder. In the form of a line dispersion it colors polyvinyl chloride foils red-violet tints of very good fastness to migration and light.

Examples 7 t0 9 I II 7 l-arnino-l(4-chloro)-benzoylamino-2zfi-dimethviolet.

oxybenzene. 8 1-amino-4-(4-methyl)-benzoylarnino-2z5-dimethblue violet.

oxybenzene. 9 l-aminoA-acetylamino-Z:5-dimetl1oxybenzene. red violet.

Example 10 A mixture of 11.5 parts of 1-amino-2-meth0xy-4- benzoylamino-S-methylbenzene, 6 parts of 2:5-diacetylamino-3:6-dichloroquinone, 3.5 parts of anhydrous sodium acetate and 500 parts of ethanol is refluxed at the boil for 5 hours, then filtered while still hot and washed with hot alcohol and water. After drying, a reddish brown powder is obtained which is 2:5-diacetylamino-3 :6-bis-(2'- methoxy 5 methyl-4-benzoylamino-phenylamino)-1:4- benzoquinone.

7.3 parts of this product are heated in 200 parts of ortho-dichlorobenzene in the presence of 3 parts of benzoyl chloride for 5 hours at 170 to 175 C., suction-filtered, and then washed with hot ortho-dichlorobenzene, hot alcohol and water, to yield 2:6-dibenzoylamino-3:7-di- .in the form of a red powder which in a fine dispersion colors polyvinyl chloride foils a red tint of good fastness to light and migration.

Example 11 A mixture of 11 parts of 1-amino-2-methoxy-4-benzoylamino-S-chlorobenzene, 5.8 parts of 2:5-diacetylamino- '3z6-dichloroquinone, 3.5 parts of anhydrous sodium acetate and 300 parts of ethanol is refluxed for 5 hours, filtered while still hot, then washed successively with ethanol and water, and dried. The resulting brown powder is 2:5-diacetylamino-3 :6-bis- (2-methoxy-4-benzoylamino-5-chl0rophenylamino)-1:4-benzoquinone.

3.3 parts of this product are heated in 150 parts of ortho-dichlorobenzene in the presence of 0.8 part of benzoyl chloride for'4 hours at 170-175 C., suction filtered, then washed with hot ortho-dichlorobenzene, hot alcohol and water, and yield 2:6-dibenzoylamino-3:7- dichloro 9:10 diacetylamino-triphene-dioxazine of the 'formula NHOOOH;

N c1- I -Nnooo.H. 0 o

(1H6 OHN, \O \\N/ 01 Nnooom in the form ofa reddish brown powder which in finely dispersed form colors polyvinyl chloride foils a strong red tint of good fastness to light and migration.

Example 12 A mixture of 18 parts of 1-amino-2-methoxy-5-chlorobenzene, 14.5 parts of 2:5-diacetylamino-3:6-dichloroquinone', 30 parts of crystalline sodium acetate and 200 .parts of ethanol of 96% strength is refluxed at the boil for hours, suction-filtered while still hot, then washed with alcohol and water and dried to yield 2:5-diacetylamino 3:6 bis-(2'-methoxy-5'-chlorophenylamino)-1:4-

NHCOGH:

V O \N/ or NHC 0 CH3 as a red powder which in fine dispersion colors polyvinyl chloride foils scarlet tints of goodfastness to light.

Example 13 A mixture of 8 parts of l-amino-2z4-dimethoxy-5- chlorobenzene, 5.8 parts of 2:5-diacetylamino-3:6-dichloroquinone, 6 parts of crystalline sodium acetate and 200 parts of ethanol of 96% strength is refluxed for 15 hours. The solid reaction product is filtered off while still hot, washed with ethanol and water and dried in a vacuum cabinet at 70 C., to yield 2:5-diacetylamino- 3 6-bis-(2' 4'-dirnethoxy-5'-chlorophenylamino) -1 :4-benzoquinone in the form of a brown powder.

A mixture of 5.9 parts of this product, parts of ortho-dichlorobenzene and 2.6 parts of benzoyl chloride is heated for 4 hours at -175 C. The precipitated pigment is filtered oil? at 100 C., purified by being washed with hot ortho-dichlorobenzene, alcohol and water, and then dried. The dark, red pigment is the 2:6-dimethoxy- 3 :7-dichloro-9: 10-diacetylamino-triphene-dioxazine of the formula NHCOCHa N o 01- OCH; 11 00- c1 NHCOCHa which in finely dispersed form colors polyvinyl chloride foils violet tints of good fastness to migration and light.

Example 14 A mixture of 6.4 parts of 2:5-dipropionylamino-3:6- dichlorobenzoquinone-(l:4), 12.6 parts of 1-amino-4- benzoylamino-Z:5-diethoxybenzene, 4 parts of anhydrous sodium acetate and 100 parts of ethanol is refluxed for 10 hours, filtered while still hot, washed with ethanol and then with water, and the residue is dried at 100 C., to yield 2:5-dipropi0nylamino-3:6-di-(2::5-diethoxy- 4-benzoylamino-phenylamino)-1:4-benzoquinone as a pale-brown powder.

4.24 parts of this product are heated in 100 parts of ortho-dichlorobenzene with 1.2 parts of benzoyl chloride for 5 hours at 170 to C. The pigment is filtered oil at 100 0., successively washed with ortho-dichlorobenzene, alcohol and water and dried. The resulting 2:6-dibenzoylamino 3 :7 diethoxy-9: lO-dipropionylamino-triphene-dioxazine forms a green powder which in the form of a fine dispersion colors polyvinyl chloride foils a bluish violet tint of very good fastness to migration and light.

Examples 15 and 16 I II 15 l-amino-4 benzoylamino-2z5-dirnethoxybenreddish blue zene. 16

1-amino-2-methoxy-4-benzoylamino-5-ehloclaret.

robenzene.

Example 17 A mixture of 3.5 parts of 2:5-dibutyrylamino-3:6-dichlorobenzoquinone-(1:4), 6 parts of 1-arnin0-4-benzoylamino-2:S-diethoxybenzene, 2 parts of anhydrous sodium acetate and 100 parts of ethanol is refluxed for 6 hours, filtered while still hot, washed with ethanol and hot Water; the residue is dried at 100 C., to yield 2:5-dibutyrylamino-3:6-di (2'z5' diethoxy-4' benzoylaminophenylamino)-1:4-benzoquinone as a blue powder.

A mixture of 4.4 parts of this product, 1.2 parts of benzoyl chloride and 100 parts of ortho-dichlorobenzene is heated for 5 hours at 170-175 C., filtered and washed with hot ortho-dichlorobenzene, alcohol and water, to yield 2 6-dibenzoylamino-3 :7-diethoxy-9: IO-dibutyrylamino-triphene-dioxazine as a reddish brown powder. A fine dispersion thereof colors polyvinyl chloride foils blue-violet tints of very good fastness to migration and light.

Examples 18 and 19 In the following table are shown further products having similar properties, obtained as described in Example 17. The base used instead of 1-amino-4-benzoylamino- 2:5-diethoxybenzene is shown in column I, while column II gives the tint of polyvinyl chloride foils colored with the dioxazine pigment.

I II

18 1-arnino-4-benzoylarnino-2z5-dimethoxybenred violet.

zene. 19 1-an1in0-2-methoxy4-benzoylarnino-5 ch1oro claret.

benzene.

Example 20 A mixture of 6 parts of l-amino-2-methoxy-4-benzoylamino-S-chlo-robenzene, 2.15 parts of 2:5-dihexahydrobenzoylamino-3 6-dichlorobenzoquinone-( l :4) and 0.8 part of anhydrous sodium acetate in 30 parts of dioxane is refluxed for 6 hours, filtered While still hot, washed Example 21 A mixture of 5.8. parts of 2:5-diacetoxy-3:6-dichl0robenzoquinone-(1z4), 13 parts of 1-amino-4-benzoylamino-2:S-diethoxybenzene, 3.5 parts of anhydrous sodium acetate and 50 parts of dioxane is refluxed for 6 hours, then filtered while still hot, and washed with dioxane and then with water. The residue is dried at 80 C., to yield 2:5 diacetoxy-3:6-di-(2':5'-diethoxy-4- benzoylamino-phenylamino)-1:4-benzoquinone as a grey powder.

4.1 parts of this product and 1.2 parts of benzoyl chloride in 80 parts of ortho-dichlorobenzene are heated for 4 hours at 170 to 175 C. At about 100 C. the pigment is filtered E, washed with hot ortho-dichlorobenzene, alcohol and water and dried, to yield the 2:6-dibenzoylamino 3:7 diethoxy 9:10 diacetoxy triphenedioxazine of the formula 0 o 0 0 Ha N o otmo- -NH0 0 can 02H 0 0 EN 0 02H! O 0 CH3 as a reddish brown powder which in a fine dispersion colors polyvinyl chloride foils strong blue tints of good fastness to migration and light.

When the condensation is per-formed with l-amino4- benzoylamino-Z:S-dimethoxybenzene instead of with 1- amino-4-benzoylamino-2:S-diethoxybenzene, a pigment is obtained which gives a red-violet coloration when incorporated in polyvinyl chloride.

Example 22 A mixture of 6.4 parts of 2:5-dipropionoxy-3:6-dichlorobenzoquinone-(l:4), 12 parts of 1-arnino-4-benzoylamino-2:S-dimethoxybenzene, 3.5 parts of anhydrous sodium acetate and parts of ethanol is refluxed for 10 hours, then filtered while still hot, washed with ethanol, then with water; the residue is dried at 80 C., to yield 2:5 dipropionoxy 3:6 di (2'25' dimethoxy 4'- benzoylamino-phenylamino)-l:4-benzoquinone as a dark grey powder.

7.9 parts of this product and 2.4 parts of benzoyl chloride in parts of ortho-dichlorobenzene are heated for 5 hours at to C., filtered and then washed with hot ortho-dichlorobenzene, alcohol and water, to yield 2:6 dibenzoylamino 3:7 dimethoxy 9:10 dipropionoxy-triphene-dioxazine as a brown powder which in a fine dispersion colors polyvinyl chloride foils redviolet tints.

Example 23 in which X represents a member selected from the group consisting of an acylamino and an acyloxy group derived from a member selected from, the group consisting of lower aliphatic carboxylic and hexahydrobenzoic acids and A represents a member selected from the groupv consisting of phenyl and naphthyl.

2. A dioxazine pigment of the formula in which n is a whole number of at most 5, Ac an acyl radical selected from the group consisting of formyl, lower alkylcarbonyl and benzoyl and Y a member selected from the group consisting of hydrogen and chlorine atoms, lower alkyl and alkoxy groups.

3. The dyestufi of the formula NHCOCHa N d 0 02H,

NHOOOH:

He 4. The dyestufi? of the formula NHCOOHa I G-OQNH /O /N -01 NH0 0 CH: 5. The dyestuxf of the formula NHG O OHzCHzCIIa NHC O OHzOHzOHa 6. The dyestuff of the formula 7. The dyestuff of the formula NBC 0 CH3 References Cited in the file of this patent UNITED STATES PATENTS 1,065,063 Maag et a1 June 17, 1913 2,086,871 Kranzlein et a1. July 13, 1937 2,948,721 Frey Aug. 9, 1960 FOREIGN PATENTS 567,538 Belgium Nov. 10, 1958 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Iatent No. 3,065, 229 November 20, 1962 Karl Ronco It is hereby certified that error appears in the above numbered patmnt requiring correction and that the said Letters Patent should read as Igorrected below.

Column 2, line 70, for "us" read use column 4, Lines 24 to 31, and column 5, lines 3 to 9, the center portion of the formulas should appear as shown below instead of as in the patent:

NHCOCH NHCOCH3 Signed and sealed this 29th day of October 1963.

(REAL) I I-latest:

lI-E'HNEST W. SWIDER Illesting Officer Ac ting Commissioner of Patents EDWIN L.. REYNOLDS 

1. A DIOXAZINE PIGMENT OF THE FORMULA
 2. A DIOXAZINE PIGMENT OF THE FORMULA 